CN111470995A - High-safety synthesis method of p-chloro-o-nitro-acetoacetanilide - Google Patents
High-safety synthesis method of p-chloro-o-nitro-acetoacetanilide Download PDFInfo
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Abstract
The invention belongs to the field of chemical synthesis, and relates to a high-safety synthesis method of p-chloro-o-nitroacetoacetanilide, which utilizes methyl acetoacetate, ethyl acetoacetate or tert-butyl acetoacetate to replace diketene in the prior art, and redefines the dosage of reactants and reaction conditions, thereby overcoming a plurality of defects caused by adopting diketene as a raw material, obtaining a p-chloro-o-nitroacetoacetanilide product with the highest content of more than 98 percent, wherein the yield can reach more than 96 percent, waste gas can be reused after three-stage condensation, a solvent can be reused, crystallized filtrate is concentrated and secondarily crystallized to recover low-content p-chloro-o-nitroacetoacetanilide, solid waste is further reduced, and the production cost is reduced.
Description
Technical Field
The invention relates to the field of chemical synthesis, and particularly provides a high-safety synthesis method of p-chloro-o-nitroacetoacetanilide.
Background
Quizalofop-p-ethyl, chemically named (R) -2- [4- (6-chloroquinoxaline-2-yloxy) phenoxy ] propionic acid ethyl ester, named gramineak, is an improved product after the removal of inactive optical isomers in the process of synthesizing gramineak.
The action mechanism and the weed control spectrum of the herbicide are similar to those of gramineous weeds, and the herbicide is absorbed by weed stems and leaves, is conducted upwards and downwards in a plant body, is accumulated on the top and in the middle of the plant body, inhibits the synthesis of cell fatty acid and necroses the weeds. Quizalofop-p-ethyl is a novel high-selectivity stem and leaf treating agent for dry farmland, has high selectivity between gramineous weeds and dicotyledonous crops, and has good control effect on gramineous weeds in broad leaf crop fields.
The p-chloro-o-nitro-n-acetoacetanilide is an intermediate for synthesizing quizalofop-p-ethyl, the main raw materials for synthesizing the p-chloro-o-nitro-acetoacetanilide at present are p-chloro-o-nitroaniline and diketene, and the reaction equation is as follows:
in the reaction for synthesizing the p-chloro-o-nitroacetoacetanilide by taking the diketene as the raw material, the obtained intermediate state is an active center of the reaction, but the strong activity of the reaction can also cause side reaction, the content of the product obtained by synthesizing the p-chloro-o-nitroacetoacetanilide by using the diketene is 88-92 percent, the yield is 70-80 percent, the main reason is that the p-chloro-o-nitroacetanilide can continuously react with the intermediate state to generate impurities besides the large reaction residue of the p-chloro-o-nitroaniline, and more importantly, the intermediate state activity is high; the method comprises the following specific steps:
in addition, diketene has strong irritation, belongs to medium toxic substances, and has severe irritation effect on eyes and respiratory tract by steam, pulmonary edema is caused by severe cases, dermatitis or ulcer can be caused by high-concentration contact with skin, cornea burn can be caused by eye contact, and liver cirrhosis can be caused by long-time high-concentration contact. And the reaction system is violently polymerized in the presence of inorganic acid, alkali and amine catalyst, and the released gas explodes the container, so that certain potential safety hazard exists, and the yield is difficult to stabilize.
Therefore, the raw material with low toxicity and high safety is adopted to replace diketene to prepare the p-chloro-o-nitro-n-acetoacetanilide, and meanwhile, the significance of improving the reaction yield and the product content is great.
Disclosure of Invention
The invention provides a high-safety synthesis method of p-chloro-o-nitroacetoacetanilide, aiming at various problems in the prior art, methyl acetoacetate, ethyl acetoacetate or tert-butyl acetoacetate are used for replacing diketene in the prior art, and the using amount and reaction conditions of reactants are redefined, so that various defects caused by the fact that diketene is used as a raw material are overcome, a p-chloro-o-nitroacetoacetanilide product with the highest content of more than 98% can be obtained, the yield can reach more than 96%, waste gas can be reused after three-stage condensation, a solvent can be reused, crystallized filtrate is concentrated and secondarily crystallized to recover low-content p-chloro-o-nitroacetoacetanilide, solid waste is further reduced, and the production cost is reduced.
In order to solve the problems associated with the prior art, the inventors replaced diketene in the prior art with methyl acetoacetate, ethyl acetoacetate or tert-butyl acetoacetate, and the corresponding reaction equation is as follows:
compared with the prior art, the reaction is milder than that of diketene, but the byproduct alcohol is separated out continuously through a rectifying tower due to the generation of the byproduct, so that the forward progress of the reaction is ensured, otherwise, the reaction speed is slow, and the whole reaction is not continued to a certain extent, so that the yield of the whole reaction is influenced, and therefore, the specific technical scheme adopted by the inventor is as follows:
a high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05-1.15 times of molar equivalent of methyl acetoacetate or ethyl acetoacetate or tert-butyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3-4h, condensing the toluene through a rectifying column and returning the toluene to a reaction bottle, condensing reaction byproducts such as methanol, ethanol or tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the condensed toluene to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely taking out the byproducts to ensure that the reaction is carried out in the forward direction;
after the reaction is finished, cooling to 0-5 ℃, carrying out suction filtration, and drying and detecting a filter cake; recovering toluene from the crystallized filtrate by reduced pressure distillation, cooling the mother liquor for secondary crystallization, carrying out suction filtration at 0-5 ℃, and drying and detecting a filter cake; combining and calculating the yield;
the waste gas generated in the reaction process is mainly toluene and contains a small amount of byproduct alcohol, the waste gas is condensed and recovered, and is washed once by using water with the volume of 0.4 time of 20-30 ℃, the organic phase carries water at normal pressure after liquid separation, the alcohol content and the water content in the organic phase are detected, the alcohol content is less than or equal to 0.5 percent, the water content is less than or equal to 0.1 percent, the product is qualified, and the product can be applied to the next batch of reaction.
In the process, reflux needs to be realized by adopting a heat-enhancing mode to promote the distillation column to collect distillate, if the voltage is increased by using a heating jacket, the temperature set by using oil bath for heating is high;
furthermore, the reaction time is 4 hours; the dropwise adding substance is ethyl acetoacetate, so that the cost can be better reduced, and the yield is improved.
Through detection, the reaction conversion rate can reach 99%, the content of p-chloro-o-nitro-acetoacetanilide obtained by cooling and crystallizing a reaction system reaches more than 98%, and the yield reaches more than 92%; the crystallized filtrate is concentrated, cooled and crystallized to obtain a secondary crystallized product, the content of p-chloro-o-nitroacetoacetanilide reaches more than 85 percent, the reduced yield reaches more than 4 percent, the total yield reaches more than 96 percent, and the method is obviously superior to the prior art.
In conclusion, the process overcomes the defects of adopting diketene as the raw material, can obtain the p-chloro-o-nitroacetoacetanilide product with the highest content of more than 98 percent, has the highest yield of more than 96 percent, can recycle the waste gas after three-stage condensation, can recycle the solvent, and can recycle the low content of the p-chloro-o-nitroacetoacetanilide by concentrating and crystallizing the crystallization filtrate for the second time, thereby further reducing solid waste and reducing the production cost.
Drawings
FIG. 1 is a schematic diagram of a reaction apparatus of the present application in a laboratory;
in the figure, toluene is condensed by a rectifying column and then returns to a reaction bottle, reaction byproducts such as methanol, ethanol or tert-butyl alcohol are condensed by the rectifying column and a secondary condensing device and then return to a shunting device, a cock of the shunting device is opened at the beginning of the reaction, and the byproducts are extracted in time to ensure that the reaction is carried out in the forward direction; waste gas is discharged through second grade condensing equipment top, when collecting waste gas and handling, reloads diverging device and tertiary condensing equipment on second grade condensing equipment, and the circulating water condensation is used in the second grade condensation this moment, and the cold brine condensation is used in the tertiary condensation.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but it should not be construed that the scope of the above subject matter is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention, and the following embodiments are all completed by adopting the conventional prior art except for the specific description.
Example 1
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97 percent, the yield is 90 percent, after toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 85 percent, the yield is 4 percent, and the total yield is 94 percent.
Example 2
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.2 percent, the yield is 90.6 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 85.7 percent, the yield is 4.2 percent, and the total yield is 94.8 percent.
Example 3
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.15 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.3 percent, the yield is 90.6 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 86 percent, the yield is 4.4 percent, and the total yield is 95 percent.
Example 4
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.2 percent, the yield is 90.8 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87 percent, the yield is 4.2 percent, and the total yield is 95 percent.
Example 5
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.5 percent, the yield is 91 percent, after the toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 86.8 percent, the yield is 4.8 percent, and the total yield is 95.8 percent.
Example 6
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.15 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, suction filtration is carried out, the filter cake is dried and detected, the content is 97.5 percent, the yield is 91 percent, after toluene is recovered from crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the suction filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.2 percent, the yield is 5 percent, and the total yield is 96 percent.
Example 7
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, suction filtration is carried out, a filter cake is dried and detected, the content is 97.5%, the yield is 90.9%, after toluene is recovered from crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, suction filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87%, the yield is 5%, and the total yield is 95.9%.
Example 8
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.4 percent, the yield is 91 percent, after the toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 86.4 percent, the yield is 5.4 percent, and the total yield is 96.4 percent.
Example 9
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating until reflux, dropwise adding 1.15 times of molar equivalent of methyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct methanol through the rectifying column and a secondary condensing device and then returning the methanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, suction filtration is carried out, the filter cake is dried and detected, the content is 97.4%, the yield is 91.2%, after toluene is recovered from crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the suction filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 86.6%, the yield is 5.4%, and the total yield is 96.6%.
Example 10
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.4 percent, the yield is 87.6 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87 percent, the yield is 3.8 percent, and the total yield is 91.4 percent.
Example 11
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.10 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.6 percent, the yield is 88.2 percent, the crystallized filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.4 percent, the yield is 4.1 percent, and the total yield is 92.3 percent.
Example 12
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.15 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.6 percent, the yield is 89 percent, after toluene is recovered from crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.4 percent, the yield is 4.1 percent, and the total yield is 93.1 percent.
Example 13
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.8 percent, the yield is 89.7 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 88 percent, the yield is 4.6 percent, and the total yield is 94.3 percent.
Example 14
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.10 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.4 percent, the yield is 89.4 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.5 percent, the yield is 4.8 percent, and the total yield is 94.2 percent.
Example 15
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.15 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.8 percent, the yield is 89.7 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 88 percent, the yield is 5.1 percent, and the total yield is 94.8 percent.
Example 16
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98 percent, the yield is 90.8 percent, after the toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.5 percent, the yield is 5.6 percent, and the total yield is 96.4 percent.
Example 17
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.10 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98 percent, the yield is 91 percent, after toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87.6 percent, the yield is 5.4 percent, and the total yield is 96.4 percent.
Example 18
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing p-chloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.15 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct ethanol through the rectifying column and a secondary condensing device and then returning the condensed ethanol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.1 percent, the yield is 91 percent, after the toluene is recovered from the crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 88 percent, the yield is 5.1 percent, and the total yield is 96.1 percent.
Example 19
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.4 percent, the yield is 92.1 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 90 percent, the yield is 4.1 percent, and the total yield is 96.2 percent.
Example 20
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.5 percent, the yield is 92.5 percent, the crystallized filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 90.1 percent, the yield is 4.3 percent, and the total yield is 96.7 percent.
Example 21
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.15 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 2 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.7 percent, the yield is 92.5 percent, the crystallized filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.1 percent, the yield is 4.1 percent, and the total yield is 96.6 percent.
Example 22
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.5 percent, the yield is 92.6 percent, the crystallized filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.6 percent, the yield is 4.7 percent, and the total yield is 97.3 percent.
Example 23
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.4 percent, the yield is 92.8 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.1 percent, the yield is 4.9 percent, and the total yield is 97.7 percent.
Example 24
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.15 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 3 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.6 percent, the yield is 92.4 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 90 percent, the yield is 4.1 percent, and the total yield is 96.5 percent.
Example 25
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.3 percent, the yield is 92.1 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.6 percent, the yield is 3.9 percent, and the total yield is 96.0 percent.
Example 26
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.10 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the reaction byproduct tert-butyl alcohol to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.4 percent, the yield is 92.6 percent, after the crystallization filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.9 percent, the yield is 4.6 percent, and the total yield is 97.2 percent.
Example 27
A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux, dropwise adding 1.15 times of molar equivalent of acetoacetic acid tert-butyl ester into a reaction system, keeping the reflux temperature for reaction for 4 hours, condensing the toluene through a rectifying column and then returning the toluene to a reaction bottle, condensing a reaction byproduct tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the tert-butyl alcohol to a shunting device,
the cock of the shunting device is opened at the beginning of the reaction, by-products are timely extracted to ensure that the reaction is carried out forward, the temperature is reduced to about 5 ℃ after the reaction is finished, the filtration is carried out, the filter cake is dried and detected, the content is 98.5 percent, the yield is 92.4 percent, after toluene is recovered from crystallization filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 89.4 percent, the yield is 4.4 percent, and the total yield is.
Example 28
Washing 30g of the waste gas condensate (toluene and a small amount of byproduct alcohol) of the 10-18 embodiments with 12g of water, carrying out organic phase reflux and carrying water for 30min after liquid separation, detecting that the ethanol content is 0.3 percent and the water content is 0.08 percent, mixing the waste gas condensate with fresh toluene, preparing p-chloro-o-nitroaniline and the mixed toluene into a solution according to the mass ratio of 1:4, heating to reflux by enhancing, dropwise adding 1.15 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4h, returning the toluene to a reaction bottle after condensation of a rectification column, returning the reaction byproduct ethanol to a shunting device after condensation of the rectification column and a secondary condensation device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 97.9 percent, the yield is 91 percent, after toluene is recovered from crystallized filtrate through reduced pressure distillation, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87 percent, the yield is 5.3 percent, and the total yield is 96.3 percent.
Example 29
Detecting toluene recovered by reduced pressure distillation of the final crystallization filtrate in example 18, wherein the detection result shows that the ethanol content is 2.3%, washing with water, separating liquid, carrying out organic phase with water, detecting that the ethanol content is 0.27% and the water content is 0.06%, mixing with fresh toluene, preparing p-chloro-o-nitroaniline and the mixed toluene into a solution according to the mass ratio of 1:4, heating to reflux with enhanced heat, dropwise adding 1.15 times of molar equivalent of ethyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 4h, condensing the toluene through a rectification column and then returning to a reaction bottle, condensing the reaction byproduct ethanol through the rectification column and a secondary condensing device and then returning to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely extracting the byproduct to ensure that the reaction is carried out in the forward direction,
after the reaction is finished, the temperature is reduced to about 5 ℃, the filtration is carried out, the filter cake is dried and detected, the content is 98.1 percent, the yield is 91.1 percent, the crystallized filtrate is subjected to reduced pressure distillation to recover toluene, the mother liquor is cooled and secondarily crystallized, the filtration is carried out at about 5 ℃, the filter cake is dried and detected, the content is 87 percent, the yield is 4.8 percent, and the total yield is 95.9 percent.
Claims (3)
1. A high-safety synthesis method of p-chloro-o-nitro-acetoacetanilide is characterized by comprising the following steps: the method comprises the following specific steps:
preparing parachloro-o-nitroaniline and toluene into a solution according to the mass ratio of 1:4, heating the solution until reflux is achieved, dropwise adding 1.05-1.15 times of molar equivalent of methyl acetoacetate or ethyl acetoacetate or tert-butyl acetoacetate into a reaction system, keeping the reflux temperature for reaction for 3-4h, condensing the toluene through a rectifying column and returning the toluene to a reaction bottle, condensing reaction byproducts such as methanol, ethanol or tert-butyl alcohol through the rectifying column and a secondary condensing device and then returning the condensed toluene to a shunting device, opening a cock of the shunting device at the beginning of the reaction, and timely taking out the byproducts to ensure that the reaction is carried out in the forward direction;
and after the reaction is finished, cooling to 0-5 ℃, performing suction filtration, and drying and detecting a filter cake.
2. The method for synthesizing p-chloro-o-nitroacetoacetanilide with high safety according to claim 1, wherein the reaction time is 4 hours.
3. The method for synthesizing p-chloro-o-nitroacetoacetanilide with high safety according to claim 1, wherein the dropwise addition substance is ethyl acetoacetate.
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| CN112961069A (en) * | 2021-02-08 | 2021-06-15 | 山东京博生物科技有限公司 | Preparation method of p-chloro-o-nitro-acetoacetanilide |
| CN113683526A (en) * | 2021-08-13 | 2021-11-23 | 京博农化科技有限公司 | Method for preparing p-chloro-o-nitroacetoacetanilide by using packed bed reactor |
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| CN113683526A (en) * | 2021-08-13 | 2021-11-23 | 京博农化科技有限公司 | Method for preparing p-chloro-o-nitroacetoacetanilide by using packed bed reactor |
| CN113683526B (en) * | 2021-08-13 | 2023-06-30 | 山东京博农化科技股份有限公司 | Method for preparing p-chloro-o-nitroacetanilide by using packed bed reactor |
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